Organic barium complexes and method of making same



Patented Nov. 4, 1952 UNI TSED PATENT ORGANIC BARIUM COMPLEXES'AND METHOD OF MAKING SAME Peter A. 'Asseffflhomas W. Mastin, and Alan Bh deS -Qleveland, Ohio, Y assignorsto The L nbrizol Corporation, Wickliffe'gQhio, a corporation o O i NmDrawing. iApplicationMaroh 16 135 1,

.ISerial No. 216,102

.35 Claims. -1 This invention relates to organic metal complexes and novel methods,of;.-produeing same. More particularly;thev :present inventionrelates to organic metal complexes which are derived from oil-solublesulphonicacids and/ orrthe barium salts thereof.

It is now recognized in the artthat-in preparing a salt or soap on an oilsoluble sulphonic acid, the use ofan excess- 0f neutralizing agent results in productswhichscontain more metal than is theoretically-requiredrtolorm the normal salt or replace the acidic hy ro n-s of the lphonic acid. The,neutra lizing;agent employed for this purpose in the priorart; has been in the form of a metal oxide, hydroxide, carbonate, etc.

Work with this type of -vproduct has shown that for many uses,.-particula-rly,.where extreme acidic soaps, the priorartworkersthen attempted to find waysof ,increasing 'the basicity of the soaps, 0r stated in another way; increasing the amount of metal, for. example, held instable form in what wastermed as ajmetal complex. One of the earliest patents referring to these basic salts as complexes or coordination compounds is McNab Nol 2, 18,894, 'who gives no indicationin hispatent asto the molecular structure of the product. As might be expectedone of the first steps. employed; toipmduce; ametal salt having an intended large excess of metal in combination A was to use ans unusually. large excess of neutralizing agent such as lime. -A.repre sentative patent disclosing this procedure is Griesinger et al: No-.,2,4 0 2,32 5, who suggested the use :oi neutralizing ;agent- 1113'; to? 220% of the theoretical amount. This largeexcess -ofneualiz ng agent wa er 'iimedint e proce m r or. less conventional for producing 'salts or soaps,

excepting that the process was carried out inlthe presen fsteamlo ie lita e b rf rm i dnof the. product.

The, work oflgriesinger wasfollowed by the wo k. of .flem e .elid iDelline ie el in Patent N o; 2,48,3,61. Thesejpatente es base their disclosure. on the. y qthes slhe min diin of an a k linee r h et l h dr x de hofi can be peptized 01;he1d. in, a state of colloidal suspension in oil by means of anoil-soluble ..m o a y sulphonate. Another worker in the art who sought to combine suchpoinplexes an excess .arnount of metal was Mertes whose Patent No. 2 ,5 0l;737 wa sgranted March 28j 1950.; Mertes first prepared the normal salt -and stated that such soap, onseap concentratej may-haveadditional base combined; therewith by'a ni ore orless simple mixing and heating operation followed by filtering; Mertes also indicatesthat his-product is similar to that of Campbell and'Dellingenin that the excess neutralizing agent was held in the product in the form of a colloidal suspension.

Allofthe previously enumerated processes have been tried, not only duplicatingcertairi-of-the examples givenin the above-identified patents, but also'usingdififerent acids and-difierentneutralizing agents. As a result of these experiments, it has been found that there is a definite upperlimitto the amount of barium metal which can be held incomposition in'colloidalsuspension bymeans of these prior art processes. The greatest total ,amountofbarium metalwhich can possibly be thus incorporated in the p fiduct by means of any of theseprior art processes has been equal. vto about 2.3 1 times; the {theoretical amou p esenti z the n im lfia F the P posesofthe present invention the ratio of the total metal in' the complex toQthe amount of metal which is in; the form pr -the normal salt of the oil-soluble sulphonic acid will hereinafter be referred to as the jfmeta'l ratio.

' .By meanspi the present -invention; it is now possible to obtain bariurn org-anic complexes which contain more; metal or higher metalratios than is possible-byprior artprocesses. i-Withregard tolubricants, theseshighi metal containing complexes are for example particularly suited, as detergents, and by reason of the metal concen- 3 tration can be used in amounts appreciably less than other additives known in the prior art in order to attain a desired level of performance. It will also be observed that by virtue of the more effective nature of the present complexes in lubricants, usually it will cost less to obtain a desired result, because appreciably less additive is required. The barium organic complexes are produced in accordance with the present invention as a fluid, which is readily adapted for ap- 1;

plication where high concentrations of barium are desired, e. g., in lubricants. For example, if the complex alone is desired, it can be produced in mineral all solutions of at least about 20% concentrations; whereas if the complex is wanted in combination with other additives, it can be available in concentrations of at least about 10% in mineral oils.

It is a principal object of this invention to provide a barium organic complex which contains in stable form an amount of metal substantially greater than that contained in any of the so-called barium metal complexes previously produced. It has been found that a metal ratio substantially greater than that possible with the prior art processes gives results which are strikingly superior, especially in the field of'lubricants in which these products have particular utility.

It is a further object of this invention to produce by our improved process complexes which while containing the same amount of barium as complexes produced by the prior art processes above-described are nevertheless different from and superior to such prior art complexes.

Still another object of this invention is to provide novel methods of producing organic barium complexes.

Further objects of this invention will appear as the description proceeds.

To the accomplishment of the foregoing and related ends, said invention then comprises the features hereinafter fully described and particularly pointed out in the claims, the following description setting forth in detail certain illustrative embodiments of the invention, these being indicative, however, of but a few of the Various ways in which the principle of the invention may be employed.

In its broadest aspects, the process of the present invention comprises combining an inorganic barium compound with an oil-soluble sulphonic acid and/or the barium salt thereof in the presence of a material which is referred to hereinafter as the promoter. The precise function of the promoter material is not specifi cally understood since it has not been possible to specifically identify the molecular structure of the product produced. At present, it appears that none of the complexes, 1. e., either those.

prepared by prior art techniques or those obtained under the present invention are susceptible of precise identification. This is clearly shown with respect to the prior art complexes by reason of the apparent disagreement among workers as to the nature of compounds which contribute metal in excess of the normal salt. In one instance, it is held that this phenomena is a result of partial replacement of the hydroml groups of the inorganic metal compound, whereas another group of prior art workers it is held that the high metal containing complexes are actually colloidal suspensions or dispersionsm which the salt of the organic acid is the peptizmg agent.

In the present invention the immediate product is produced by the use of a promoter and at least at one stage contains the promoter in chemical combination. It is possible, however, to re- 1 cover the promoter from the product by suitable treatment as hereinafter explained and the final product, which then has a constitution different from the initial product, is similar to the initial product, of utility as a lubricant additive.

More particularly, the present invention comprises the process of producing a metal complex by combining an oil-soluble sulphonic acid and/or the barium salt thereof, a promoter, and an inorganic barium compound.

In a more specific aspect, the present invention is concerned with salt complexes which are prepared by the method comprising:

I. Preparing and mixing a mass in which, at 50 C., at least 50% of the components are in the liquid state, and in which mass the active components consist of A. An oil-soluble component selected from .the class consisting of:

(1) The sulphonic acids;

(2) The barium sulphonates; and

(3) Mixtures of (1) and (2) B. An organic compound containing an element of group VI of the periodic table having an atomic number less than 17, which compound is selected from the class consisting of:

(1) Organic compounds Ali, in which H is hydrogen and A is an anionic radical, which compounds:

(a) Are water-soluble at a temperature of 50 C. to the extent of at least 0.0005%;

(b) In the presence of water at about 25 C. have an ionization constant greater than about 1 l0- and (c) In saturated aqueous solutions at about 25 C. have a pH not greater than about 7;

(2) The barium salts vof such organic compounds;

the relative amounts of A and B used being in the range of from about one equivalent of A to about 10 equivalents of B to about 10 equivalents of A to about 1 equivalent of B;

C. An inorganic barium compound;

(1) Which is water-soluble at a temperature of 50 C. to the extent of at least about 0.0003%; and

(2) In an amount such that there are present in the mass substantially more than one equivalent of barium, including the barium present in the remaining components, per equivalent of A plus B;

D. Water, including free and combined water in the other components, in an amount which is equal to at least one mole per 65 mole of C.

II. And then maintaining the mass at a temperature and for a period of time sufiicient to drive off substantially all free water and water of hydration which maybe present.

Optionally, the above salt complex can be further modified by:

the mass will form a material having'a higher "salt'fup to man tirn esjthat met-nu 3 complexes.

' reflux temperature.

ionization constant-'1than-r-theimetal-free-:form of promoter, "*to liberate in' the?- form -of-zan ionizable organicr'compoundra substalntial portion' of-theanionic "radicalof the :compound EB given above.

"If' desired; the salt complex preparedfin accordance with Step III canthenundergo treatment to:

IV. Remove from the. mass so. .much-:of-- B(1) above as may have .beenregenerated aby Step .III.

The following examples giv v. V A: w r s eret oi -a plurality of products "whcQh lraiijg ein etal content from-*about' thiat of e ormal-man We have found that sul content-values}andf the culated' therefromgarefonef of: the niost rehabIe means for characterizing certain -of -thesalt As the description-of--'t-h proceeds, it will become apparen that the neutralization" numberpf a salt ompl'ex'- is in certain 'instanoes' 'an unreliablef hqg ej 'fthe amount of excess metal-insuchcomplexi since it isgreatly 'af fected 'by the' type of rinorganie barium compound employed and ean be varied within Wide limits i without "significantly? changing the metal content of theproductby treatment of the mass with air, CO2, or the like.

The above is not to be construed as a statement that the neutralization number is not-an important property of'asalt'complex. Forsome uses, for example in-lubricants, it is advantageous'in certain instances to employ-a salt complex-of a substantially neutral character, whereas in other instances a salt-com'plexof high alkalinity has been found to produce thedesired results.

1980 grams of the 'barium saltof "'petrola-tum sulphonic acid (which contains 912% "sulphate ash and is derived from Pa. -a1nber petrolatum) and 132 grams of para-ter'tiary-butyli phenol (ratio of equivalents ofsulphonate to phenolic compound is 1.54), were placedinto a 5-liter, 3-neck flask and heatedto 95" C. *"To thismixture was added a barium oxide slurry (417 grams 'of barium oxide and 1100 grams-of water)- and the mixture was heated forabouton'e hourat Then the temperaturewas slowly raised to about ISO-160 C. and main- "tained there for one hour" to remove substantially all of the water. The product was then filtered. The salt complex is a 'vis'cous*liquid, light brown in color, and having averys'light The above preparation;-which is an example of the present invention; is compared :with a basic sulphonate prepared in accordance-with a conventional technique.

' "500. gramsgof the; bariumzsalt of the petrolatum sulphonic: acidsgivenqin-Example 1:;where mixed with; a" slurry of :barium goxide (containing 3 8 (grams .ofvbarium 'oxide and 50 ggrams-bfi water) :and; placed: in a- 2 -liter,- 3-neck' flask, heated at about 160 vC. for one hour untilsubstantially iall-of the water -was removed, andwthen -the product is filtered. -'I he'-- resultant ibasic sulvphonalte' -has-;:the= -f,olloWi-ng--:properties:

* asi 5-327 'Percent sulfate ash e 9285 ""Metal' ratio --108 EXAMPLE 3 "109 grams of the barium saltof unsaturated .i-paraiifin wax sulphonic acid" containing- 13.1% sulfate ash were mixedwith 4 55 g-rams o f a mineral oil having a viscosityof 160 SSU at 100 F. I and 109*.5 'gr'amsof p'ara tertiary butyl phenol f (Tat/i0" of equivalents is 41:54); "placed" in a'suitable vessel 1 and heated to about with stirring. To this mixture-was'added a slurry of barium oxide (containing 269 grams of barium oxide and, 920 grams of water) and the total mixture wasiheated at about C. for about one hour. "The temperature was slowly" raised '1tofabout'1'50 (Land held therefor about one hour until substantiallyv all of the water was "removed. "Then'about 3% Hyflo (afilter-aidl wasadded to the product to facilitate filtering. "The" salt complex was "then "separated" from the' product f by filtration. The salt complex thusprepared had the following properties:

Clear -Clear I The salt complex 1 product was *fiuidflbioivn in '-"color,-' and'- did not contain any odor.

"The preparation given in Example- 3 is a typical illustration' ofthe present invention. F In- Example 4- given below a basic sulphon'ate was prepared in *accordance 'wi-th' a conventional technique for comparison with the product giveniin Example 3.

511 grams 'o f' thbarium salt or: unsaturated .60 parafiin wax sulphonic-a'cid given in Example 3 were mixed with 75 grams of water and heated j to, about"60'C.' withstirring. '58" gramsofi barium oxidew'ere' added tdthe inixturewhi'ch was then heated to'ab'out"150 'Cia'ndfhelcfthere for one hour until substantially all of I the water was remo'ved. Y The product was then filtered withthe I aid ofl-lyiio in orderto separate the complex salt. The salt complex possessed-the following properties:

Basic No V 1 16.2 "Percent sulfate ash ;."'19.7 Metal" ratio 1 .63

75 did not contain any ed EXAMPLE5 1000 grams of the barium salt of mono-paraffin wax substituted naphthalene sulphonic acid containing 8.63% sulfate ash weremixed with 445 grams of mineral oil having a viscosity of 160 SS at 100 F. and 64.5 grams of para-tertiary butyl phenol (ratio of equivalents is 1.7) and heated to about 90 C. A slurry of barium oxide (203.5 grams of barium oxide and 543 grams of water) was added, and the mixture was heated for two hours at a reflux temperature of about 165 C. for a period of about one hour. Hyflo" was then added to the product and the salt complex was recovered by filtration. The salt complex possessed the following:

Basic No 44.1 Percent sulfate ash 17.9 Metal ratio 2.37

The salt complex prepared in accordance with Example was compared with a product which was made by a conventional technique, as shown in Example 6 below.

EXAMPLE 6 1000 grams of the barium salt of mono-paraffin wax substituted naphthalene sulphonic acid given in Example 5 were heated to about 95 C. and barium oxide slurry (115 grams barium oxide and 100 grams water) was added to the mixture. The total mixture was held at a temperature of 100 C. for about one hour, and then dehydrated at a temperature of about 150 C. for about one hour. The salt complex was separated by filtering the product. Throughout the above preparation a nitrogen atmosphere was maintained above the mixture. The resultant salt complex was liquid and black in color. The following pro erties were determined for the product:

EXAMPLE 7 400 grams of the barium salt of mono-paraffin wax substituted naphthalene sulphonic acid disulphide containing 8.2% sulfate ash and 27 grams of para-tertiary-butyl phenol (ratio of equivalents is 1.54) were placed in a suitable vessel and heated to 90 C. A barium oxide slurry constituting 66.5 grams of barium oxide and 180 cc. of water was added to the mixture and refluxed for about one hour. The temperature was then slowly raised to about 160 C. over a period of about four hours and held at that level for about 1.5 hours until substantially all of the water was removed. The salt complex was separated by filtering. The following properties were determined for the salt complex:

Basic No 69.7 Percent sulfate ash 24.3 Metal ratio 3.50

The product obtained in accordance with Example 7 was then compared with a salt complex obtained under a conventional technique as shown in Example 8 below.

EXAMPLE 8 20 ml. of water were added to 450 grams of the barium salt of mono-parafiin wax substituted naphthalene sulphonic acid disulphide given in Example 7 and heated to a temperature of about 60 C. 27.5 grams of barium oxide were then added to the mixture and the temperature was slowly raised to about 160-170 C. and held there for about one hour until substantially all of the water was removed. The salt complex was then separated by filtration. The product was fluid in consistency, black in color, and contained a slight odor. The following properties were determined for the product:

Basic No 5.27 Percent sulfate ash 8.95 Metal ratio 1.10

It is to be noted that the barium salt of mono paraflin wax substituted naphthalene sulphonic acid disulphide has a sulphate ash of about 8.2% and that the complex formed by the conventional technique did not increase the metal content appreciably. However, as shown in Example 7, the method of the present invention produces a complex containing substantially more metal in combination.

Other types of oil-soluble metal sulphonates were used in the method of the present invention. In the following examples, para-tertiary-butyl phenol was employed with difierent oil-soluble metal sulphonates. It is to be noted that in every instance a salt complex was formed containing more metal than is possible by known techniques.

EXAMPLE 9 6000 grams of a 30% by weight oil solution of barium petroleum sulphonate (sulphate ash content 7.6%) were mixed with 348 grams of paratertiary-butyl phenol (ratio of equivalents 1.70) is a 12-liter, 3-neck flask and heated to 95 C. A slurry of barium oxide constituting 1100 grams of barium oxide and 2911 grams of water was then added and the mixture held for about one hour at a temperature of about -95 C. The total mixture was then slowly raised in temperature to 150 C. and dehydrated at that temperature over a period of about 4 hours. The salt complex was separated by filtration and was found to be slightly viscous liquid, black in color, and did not contain any odor. The properties of the salt complex were as follows:

Basic No 72.1 Percent sulfate ash 23.1 Metal ratio 3.59

A mixture of different oil-soluble metal sulphonates was treated in accordance with a conventional technique and by the method of the present invention to determine what effect, if any, the two types of sulphonates would have on the quality of the product. Such preparations are given in Examples 10 and 11 below.

EXAMPLE 10 A mixture containing 500 grams of the barium salt of petrolatum sulphonate acid (sulfate ash 9.2%), 197 grams of the barium salt of petroleum sulphonic acid (sulfate ash 7.6%), and 50 grams of para-tertiary-butyl phenol (ratio of equivalents of sulphonate to phenolic material is 1.54) was heated to C. A slurry of barium oxide constituting 123 grams of barium oxide and 330 grams of water was added to the mixture. The total mixture was refluxed for one hour at C. and then the temperature was slowly raised to C. fora period of one hour to substantially remove all the water. The complex was separated by filtration and was found to be a liquid,

93;? and black in color? The-following properties were determined 1.:

Basic -N01; 1 27.7 Percent sulfate ash 17.25 Metal ratio 2.41

EXAMPLE 1 1 By the conventional technique; 480 grams ofthe barium salt of petrolatum sulphonic acid and 200 grams of the-barium salt of-petroleum sulphonic acid of Example were mixed witha barium oxide slurry containing 68*grams of waterand 60.8 grams of barium oxide; The com ponents were heated to a temperature of- 1601-0.

for one hour until substantially all the water was removed. The desired complex was separated by filtration and was found to be a viscous liquid, light brown in colon-and contained a slight odor. The following properties .were determined Basic No. 2 20.2- Percent sulfate ash; 1172' Metal '-ratio 1.51

The complexes of. this, invention.can, -be also obtained by using a mixture of oil. soluble organic acids and the barium salts thereof. Thefollowe ing .example. illustrates this concept.

2875 grams ofpetroleum sulphonic .acid and-- 6000 grams of a %oil solution of barium petroleum sulphonate (sulphate -ash-is-7.6%-) were mixed with-553.7 grams of para-tertiary- 'butyl phenol (ratio of equivalents -is--1.60). The mixture was heated toabout-50 C. whereupon a slurry of BaO (consisting of 2027.6 grams of BaO and 5395' grams of water) was added and the mixture was thenmaintained 'at 'a temperature of about 90-95 0. for an-additionalhour. Upon;-

inspection the mixture appeared thoroughly mixed,- therefore the-temperature was-slowly raised to -150--C. and held -there forapproximately onehour.

lows:-

Basic No 73.0 Percent sulfate .ash 23.3 Metal ratio 3.73-

While most of the examples given herein. use eitheraneutral or normalsalt of 'theorganic The-product analyzed as-fol acid asnastarting. material to produce the. high metal content complexes, nevertheless it is contemplated in this invention-to'employ as a starting material the overbased salts; or complexes W e: pr paredaccording-to; conventional; hn ques; ,T e f llow n xamp1e:;i11ustrat s this concept:

EXAMPLE .13

163.4.grams of abariu p troleum sulphonate BaQcomplex (obtained by dehydrating .a barium petrol'eumsulphonate having a 7.6.%.-.sulfate ash, water, andBaO mixture at 150 C. for one hour, and producing a complex which has -a basic num ber vof..40,.metal ratioof- 2.25; and a 16% sulfate ash) and 121 grams of diisobutyl phenol- (ratio of equivalents 1.7) were combined and heated to 70- C., To this. mixture. were added .665, cc. of. water, followedby a. slow. addition ;of 175 .grams ofgBaOL The entire. mixturewas then refluxed for one hour, and the ternperature was raised to 150 C. over a 3 hourperiodand held there for one hour. Prior, to: filtering; the mass wasblown with COZ-ata rate of 3.6m, ft./hr.:for 1% hours-;

at 150 C. The. product analyzed: as follows Basic No 8.67

Percent sulfate ash 24.8

Metal ratio; 4.1a

EXAMPLE 14 2000 grams of a 30% oil solution of barium petroleum sulphonate (sulfate ash 7.6%) were mixed with 120 grams. of para-tertiary butyl phenol (l.52 ,ratio ,of, equivalents), and heated to C. To said mixture .Wasadded a slurry of barium oxide containing520grams of barium oxide and 1390 ml. of water. The total mixture was heated for one hour at C., and thenwas slowly raised in temperature over a period of three hours to 200 C. The mixture was maintained atthishigh temperaturefor a period of one-half hour. The salt complex was separated by filtering and-was found to be an oily liquid, reddish-brown in color, and contained a faint odor. The following properties weredetermined:

Basic No. 71.5

Percent sulfate ash 24.3 Metal. ratio 3. 80

EXAMPLE .15.

2035 grams of 30% 'oil'solution of barium petroleum sulphonate (sulfate ash 7.6%) were mixedgwith 74,5 grams of -phenol (l.67 ratio of equivalents) and heated to, .100? C. A barium oxide slurry containing 483grams 10f bariumoxide and 1290 ml. of water was .addedandthe' mixture refluxed slowly for .a .period ofzone hour at 100C. The miXturewasLthen dehydrated by heating slowlyto 200: C. and. maintaining such a temperature for a -period of about onehalf hour. The sa1t=complexwas separated by filtration and was-;-found --to' --'be an oily liquid,

reddish-brown in color, and contained a slight odor. The following properties were determined for the complex;

Basic No 111.5 Percent sulfate ash; 32.8 Metal ratio 5.56

In addition to the promoters tested above,

various other types were tried tq deterrnine the i effectiveness thereof in forming salt complexes...

EXAMPLE 16 1 630 grams of a 30%oil solution ofbarium pee troleum sulphonate (7.6% sulphate ash); were admixedwith 350 grams, ofirnitroparaffiri wax (ratio of equivalents is 0.159.). Then'.760.:1cc.' of water were added, followed by-the. addition. of 296 grams of BaO. For one:h-our. .the;mixture was agitated at 90-l00 C., whereupon the temperature was raised to C. and held at that-level for one hour. Themixture wasfiltered,

and the complex obtained had the followin properties:

Basic No 132 Percent sulphate ash 33.3 Metal ratio 6.47

EXAlVIPLE 17 1500 grams of a 30% oil solution of barium petroleum sulphonate having a sulfate ash of 7.6%, 93 grams of iso-propyl phenol (ratio of equivalents 1.7) and 670 grams of water were placed in a 3-liter flask and heated to 60 C. 250 grams of BaO were then added, and the temperature was allowed to rise to 100 C. The mixture was held at 100 C. for one hour, followed by a rise in temperature to 150 C. over a 2 hour period, where the temperature was held for one-half hour. The total mixture was filtered, and the end-product had the following properties:

Basic No 87.8 Percent sulfate ash 25.95 Metal ratio 3.88

EXAMPLE 18 1140 grams of a 30% oil solution of barium petroleum sulphonate having a sulfate ash of 7.6% and 80 grams of paratertiary-amyl phenol (ratio of equivalents 1.54) were heated to 70 C. Thereafter 600 cc. of water were added, followed by a slow addition of 227 grams of BaO. The mixture was refluxed for one hour, and then the temperature was raised to 160 C. over a period of four hours and held there for onehalf hour. The product was separated by filtration and had the following analyses:

Basic No 85.5 Percent sulfate ash 24.60 Metal ratio 3.96

EXAMPLE 19 2583 grams of a 30% oil solution of barium petroleum sulfonate having a 7.6% sulfate ash, 144.2 grams of beta-naphthol (ratio of equivalents is 1.69) and 1262 ml. of water were combined and mixed thoroughly. Then 472 grams of BaO were added over a 1 hour period, followed by maintaining the total mixture at 100 C. for 1 hour. The temperature was then raised to 150 C. and held there for 1 hour. Prior to filtering the mixture, it was blown with CO2 for 75 minutes at which time the mixture had a basic number of 0.8. After filtering, the product analyzed as follows:

Basic No 4.88

Percent sulphate ash 23.8

Metal ratio A 3.90 EXAMPLE 20 1530 grams of a 30% oil solution of barium petroleum sulphonate having a 7.6% sulfate ash. 129 grams of iso-nonyl phenol (ratio of equivalents is 1.7) and 727 ml. of water were combined and thoroughly mixed. Then 271 grams of BaO were added and the total mixture was held at 100 C. for 1 hour. The temperature was then raised to l50-l60 C. and held there for 1 hour. Prior to filtering, the mass was blown at about 150 C. with CO2 until a basic number of about 1 was obtained. The filtered product analyzed as follows:

Basic No 3.9 Percent sulphate ash 25.0 Metal ratio 1.17

12 EXAMPLE 21 2600 grams of a 30% oil solution of barium petroleum sulphonate having a 7.6% sulfate ash. 215 grams of tertiary-butyl chlorophenol (ratio of equivalents is 1.7), and 1265 cc. of water were combined, followed by an addition of 459 grams of BaO. The temperature of the total mixture was raised to C. and held there for 1 hour. Then the temperature was raised to 150 C. where it was held for 1 hour. Prior to filtering the mixture, it was blown for 3 hours with CO2 at -145 C. until the mixture was slightly basic. The filtered product analyzed as follows:

Basic No 13.3 Percent sulfate ash 25.45 Metal ratio 4.38

EXAMPLE 21 2600 grams of a 30% oil solution of barium petroleum sulphonate having a 7.6% sulfate ash, 215 grams of tertiary-butyl chlorophenol (ratio of equivalents is 1.7), and 1265 cc. of water were combined, followed by an addition of 459 grams of BaO. The temperature of the total mixture was raised to 100 C. and held there for 1 hour. Then the temperature was raised to 150 C. where it was held for 1 hour. Prior to filtering the mixture, it was blown for 3 hours with CO2 at 135- C, until the mixture was slightly basic. The filtered product analyzed as follows:

Basic No 13.3 Percent sulfate ash 25.45 Metal ratio 4.38

EXAMPLE 22 1530 grams of a 30% oil solution of barium petroleum sulphonate having a 7.6% sulfate ash and 210 grams of trichlorodiphenyl ether sulphonic acid (ratio of equivalents is 1.7) were heated to 70 C. To this mixture were added 725 grams of water, followed by the addition of 271 grams of BaO. The entire mixture was refluxed for 1 hour, then heated to C. over a 3 hour period and held there for 1 hour. Prior to filtering, the mixture was blown with CO2 at 150 C.

and at a rate of 3.6 cu. ft./hr. for 1 /2 hours. The filtered product analyzed as follows:

Basic No 0.45 Percent sulfate ash 24.7 Metal ratio 4.34

EXAMPLE 23 1530 grams of a 30% oil solution of barium petroleum sulphonate having a 7.6% sulfate ash and grams of tertiary-butyl naphthalene sulphonic acid (ratio of equivalents is 1.7) were combined and heated to 70 C. To this mixture were added 725 grams of H20, followed by a slow addition of 271 grams of BaO. The entire mixture was then refluxed for one hour, and then heated to 150 C. over a 3 hour period. The mixture was held at 150 C. for 1 hour. Prior to filtering, the mass was blown at 150 C. with CO2 at a rate of 3.6 cu. ft./hr. for 1% hours. The filtered product analyzed as follows:

Basic No 0.41

Percent sulfate ash 24.1

Metal ratio 4.12

EXAMPLE 24 1530 grams of a 30% oil solution of barium petroleum sulphonate having a 7.6% sulfate ash and 131 grams of methyl naphthalene sulfonic 13 acid (ratio of equivalents: is'il.7;) were combined and heated to.70? C... 725 grams of water,were added to the -mixture;1followedby a slow "addition of. 271 gramsiof BaOL The entire mixturetwasrefluxed for '1 hour,;: then the. temperature was raised to 150 C. over a' three hour' period, and

held there for one hour: Prior to filtering, the

mass was blown'with CO2 at a rate of 3.6 cu. fir/hr;

for 1 /2 hours at'150 C. The filtered product analyzed as follows:

Basic No.- Nil Percent sulfate ash; 25.9: Metal ratio-.1 4.4-1

EXAMPLE 1530 grams of a oil solution of barium petroleum sulphonate having a-7.6 sulfate ash; 113' grams of "diisobutenyl" sulphonic' acid (ratio of equivalents'is" 1.7) and 725 *grams" of H20 were combined and heated to 70? C. To this'mixture were added 271v grams .of Ba-O; and-the entire mix.

tureiwas'heated at 100 C. for 1 hour.- The mix-.

ture-was then heated-at 150C. for one hour; fol-:- lowed by blowing with CO2 at 150 C. prior to:

filtering; to obtain a substantially neutral mass; The filtered, product analyzed .as follows Basic No 0.23 Percentsulfateash; 24.6

Metalratio 4.10

EXAMPLE 26 Di-isopropyl benzene sulphonic acid, obtained by reacting 162 grams'of di-isopropyl benzene with 122 grams. of chloro sulphonic acid for 1 hour at 100 'C., was combined with2600grams of a 30% oil solutioniof. barium petroleum sulphonate' having a 7.6% sulfate 'ash and l220m'l. of water. The ratio of equivalents of oil soluble sulphonate .to sulphonic acid is 1.7. Then 461 grams of BaO were added slowly and the mixture held at 100 C. for 1 hour. The temperature was raised to 150 C. and held there for 1 hour; Prior,

to filtering, the mixture .was blown with CO2 for A hour at 120-140 C. The filtered product analyzed as follows Acid No 1.22

Percent sulfate-ash 2514 Metal ratio' 4.3

EXAMPLE 27 Cymene sulfonic acid, obtained'by re'acting'134' grams of 'cymene with 122 grams'of'chlorosul honic acid at 70-100 C. for 1 hours, was com-. bined with 2600 grams of a 30% oil solution ofbarium petroleum sulphonate having 9.76% sul fate ash and 1220 ml. of water. The ratio equivalents of oil soluble sulphonate to sulphonic acid is 1.7. To this mixture-were added 461 grams of BaO, and. the entire .mixturexwas then. heldgat 85--100- C. for-lhour." Then the temperature was raised-to 150 C. and held there for "1 hour."

Prior tofiltering, the mass was blownwith CO2 for hour. at 130 C. Thefiltered product ana.-.

lyzed as follows:

Acid No 0.95

Percent sulfateash 25.8

Metal: ratio; 4.38:

EXAMPLE 28 2600 grams of a 30% oil solution of barium pe troleum sulphonate having "a 7.6% sulfate ash,

2219 grams of tertiary butyl dichlorop-henol (ratio of equivalents is 1.7) and 1265 grams of water fort'l hour.

were combined; followe'd by an additiorrof 45-9 grams of B'aO- over-a- 45-'minute' -period5- The en-' tire mixture was held-'at100'-C.'for"1 hour-,"fol-- lowed by maintaining the temperature at 150 C;

Prior to filtering, the masswasblown; with CO2 for minutesat 135-150 cguntilithe mass was slightly, acidic. The. filtered product analyzed as follows? Basic No; -645 Peroent-sulfate'ash 23.2

Metal ratio; 3.85

EXAMPLE 29 a Acid. N Percent:.bariumxunmm 1425.: Percent sulfate ash 24.2. (calculated from metal content) Meltal'ratio'" 4:15;

EXAMPLE 30 2600 grams of ar'30%="-oilsolution of barium petroleum sulphonate having a 7.6% sulfate ash,

grams. of Yacetyl' acetone (ratio of equivalents is'1.'7). andfl265'ccxof water were combined, followed byfaslow'addition of 459 .grams of :BaO over a. 1 hour fperiod: The" entire mixture "was heldat 94 'C."for' 1 ;hour,"fo llowe'd .by-a 1 hour. period of iheatinggat "150 C.' Prior "to filtering," the mass was'blown'with COz'for 1 hour'at CZ'. The filtered 1 product analyzedf'as; follows:

Acid No; 0.2 Percent: sulfate ash 22.8 Metal I'atiO" 348 EXANIPLE 31 1530 "gramsof a- -30'%" oil solution ofbarium :petroleum -sulphonate having a 7.6 sulfate ash and" 206" grams of di-t-butyl naphthalene sulphonic acid (ratiorof equivalents is 1.7) were combined. and heated.to.70 C. 725 grams. of water were then added,"followed by a slow addition of 1271 grams of BaO; Themixture was.re-'- fluxed for. l'h'our, and ith'enheld .at 150 C." for 1 hour. Prior. to filtering, the mixture-was blown withLCOi at'arate of 3.6 cu. ft'./hr. for.1.25. hours at latemperaturepof150? C. The filtered product analyzed .as folloiwszi.

Percent sulfaterzash 1 .23-.-'6

Metal." ratio; r 4:12 EXAMPLE'BZ" Asm'ixturewof- 2280-gr-ams-. of -a z 30 toilv solutionv of barium -p,etro1eumsulphonate (sulfate ash- 7.6%) and 83 grams of phenol (ratio of equiv-- alents is 1.53) was heated to a temperatureeof 60C. 496 grams of barium oxiddandfliillOErams,

of water were-added tothe above mixture'and'; the temperature'was raised'to'90-100C." After holding at 'sa-id temperature for one hour. the temperature was raised over a period of three hour. The resultant salt complex was fluid in consistency and dark red-in color. .The following properties were determined:

Basic No 91.4

The promoter employed in this test was prepared by reacting 80 grams of tertiary butyl benzene with 71 grams of chlorosulphonic acid at a temperature of -40" C. for a period of one hour. The resultant product, tertiary butyl benzene sulphonic acid, was dissolved in a little warm water and admixed with 1550 grams of a 30% oil solution of barium petroleum sulphonate (ratio of equivalents of sulphonate to sulphonic acid is 1.52). The mixture was heated to 90 0., whereupon 284 grams of barium oxide and 260 ml. of water were added. The mixture was stirred for one hour at a temperature of 100- 102 C. The temperature was thereupon raised to 200 C. for a short period and then reduced to 150 C. and held at that level for a period of one hour. The salt complex thus obtained was an oily liquid, reddish-brown in color, and contained a faint odor. The properties of the product are as follows:

Basic No 64.7

Percent sulfate ash 27.0

Metal ratio 4.73

EXAMPLE 34 2500 grams of 30% oil solution of barium petroleum sulphonate (sulfate ash 7.6%) were admixed with 173 grams of para-tertiary butyl benzoic acid (1.68 ratio of equivalents) and heated to 95 C. 458 grams of barium oxide and 1215 grams of water were added to the mixture and the temperature was maintained at 100 C. for about one hour. Thereafter the temperature was slowly raised to 150 C. and maintained at that level for a period of one hour. The salt complex was filtered from the total mixture and was an oily liquid, brown in color, and contained a faint odor. The following, properties were determined:

Basic No 32.1 Percent sulfate ash 19.1 Metal ratio 2.88

EXAMPLE 35 2050 grams of a 30% oil solution of barium petroleum sulphonate (sulfate ash 7.6%) were admixed with 73.5 grams of l-nitro propane (ratio of equivalents is 1.62) and heated to a temperature of 95 C. 388 grams of barium oxide and 1035 ml. of water were added to the mixture and the temperature was maintained for a period of one hour at 100 C. Thereafter the temperature of the mixture was slowly raised to 150 C. over a period of 2 /2 hours and maintained at that level for a period of one hour. The product was filtered to separate the salt complex. The desired product was an oily liquid, reddish-brown in color, and contained a slight odor. The following properties were determined for the product: Basic No 78.2 Percent sulfate ash -28.2 Metal ratio 4.60

Another experiment was performed in which the promoter was in the salt form. Example 36 below illustrates this feature of the invention.

EXAMPLE 36 1700 grams of a 30% oil solution of barium petroleum sulphonate (sulfate ash 7.6%) were admixed with grams of barium phenate (ratio of equivalents is 1.7) and 570 grams of water. The mixture was heated to 75-100 C. whereupon 214 grams of barium oxide were added. The temperature of the mixture was maintained at 100 C. for one hour and then raised slowly to 150 C. and held at this level for a period of one hour. The salt complex was then separated from the product by filtration and was found to be a viscous liquid, light brown in color, and contained a slight odor. The following properties were determined for the salt complex:

Basic No 68. Percent sulfate ash 21.4 Metal ratio 3.23

The salt complex can also be prepared by starting with the oil-soluble sulphonic acid and combining therewith the promoter and the inorganic metal compound. This technique differs from those given above, because as shown in all the above examples, the normal metal sulphonate Was employed as a starting material. In order to demonstrate that the metal ratio of the salt complex obtained by this method is greater than by conventional techniques, a comparison was made therewith, in which experiments the acid was employed as a starting material. In this respect, Examples 37 and 38 below are illustrative.

EXAMPLE 37 The oil-soluble petroleum sulphonic acid employed in this test was derived by reacting a 60% oil solution of sodium petroleum sulphonate with the stoichiometric amount of sulfuric acid (96% strength) at a temperature of 60-70% C. for a period of two hours. After allowing the mixture to stand for about 12 hours, it was filtered twice through a glass cloth. 2875 grams of the product just described were combined with 205.7 grams of tertiary butyl phenol (ratio of equivalents is 1.39), 1647 grams of low viscosity mineral oil having a viscosity of about SUS at 100 F., 927.6 grams of barium oxide and 2480 grams of water and heated for one hour at a temperature of 98 C. The mixture was then dehydrated for one hour at a temperature of C. so as to remove substantially all of the water. The product was a viscous liquid, brown in color, and contained a mild odor. The following properties were determined for the desired product:

Basic No 74.2

Percent sulfate ash 24.4

Metal ratio 4.02

EXAMPLE 38 500 grams of the oil-soluble petroleum sulphonic acid iven in Example 37 above were heated to 75 C. 55 grams of water were then added and followed by a slow addition of 162.2 grams of barium oxide. The total mixture was maintained at a temperature of 150 C. for a period of one hour. The desired complex was separated by filtration and was found to be a very viscous liquid, black in color and did not contain any odor. The following properties were determined for the product:

Basic No 53.7 Percent sulfate ash 25.65 Metal ratio 1.74

17 Itwas indicated hereinabove that the saltcomplexes of the present invention can be prepared byfirst adding water to themixture'ofthe' ilsoluble metal "sulphonate and/ or sulphonic acid and promoter, and'then adding the inorganicmetal' compound in a dry" state. In' this" respect, Example 39 given below illustrates an'alternative method by which "the "salt complex "can be prepared.

EXAMPLE 39 IOOQgramsof the barium saltof diparafiin wax substituted phenol. sulphonic acid (sulfate'ash 6.6%) were admixed with- 55,,grams :of, paratertiaryv butyl phenol .(ratio. of equivalents .is-.1.54) andheated to a temperature-M90 C. .1800 cc. of water werethen added. The mixture was mixed thoroughly and then 300; grams of dry. barium oxide were .added. The total. mixture :Was .refiuXed for :two hours. followed by. an addition of 573, grams ofa mineral-oil having. a viscosity f 160881] at 100 F. v'Ihe temperature. was raised over .a, period of four hours to 170 ;C.iand'then maintained there for one hour. .The salt complex was obtained by filtering" the product and was foundlto .be a;.viscous.;liquid,idark brown in color, and contained a faint odor. :.The .propertiesothe saltcomplexareas follows Basic'No. 67.8 Percent sulfate ash ""2318 Metal ratio 2167 .Another method .of preparing :the organic barium complexesis to. treat the mass, prior; to filtering; with an acidicmater-iaLand then filtering same to recover the; desired: metal. complex. The steps of preparation, prior'to treating :with the acidic material, can be any of those discussed herein. The following examples illustrate such a method of producing'the complex and serveas a comparison to show "the improvement over methods of preparation not employing the treating step withtheacidic material. I

EXAMPLE 40 'l700, grams of a 30% all solution of. barium tained. The-following properties of the -:product were determined:

Basic No 1 66.0 Percent sulfate ash 222 Metal ratio 3.64

' EXAMPLE 4:1

1700;,gramsof a-30 oilvsolution ofqbarium petroleum sulphonate having. a 7 .6-% 4 sulfate ash were mixed with 134 grams of di-isobutyl-phenol (ratio of equivalents is 1.7) and heated to 70 C. 302 grams of BaO and 800'cc.-of water were then added thereto, and the total mixture refluxed for aboutl hour. .The temperature wasthen raised to 150 C. overa periodof 1% hours, and held at that level for l-=hour. The mixture was then blown with COzatatemperatureof 150 C.-and at a rate of 1650 cc./minute for 38 minutes,-.-an d the mixture possessed-abasic No. of'1.47. The mixture was then filtered and the desired complex acidic.

is obtained. The following properties were" determined Basic No 5.05 Percent sulfate ash 26.0 Metal ratio 4.52

From'the' two examples given above "it can be seen from the sulfateash analyses of theproducts that CO2 blowing prior tofilt'ering increasedthe metal content significantly.

The" example below illustrates the. utility ofSOz in this respect.

' EXAMPLE 42 4590 grams-of a 30% oil solutionofbarium petroleum sulphonate having ,a sulfatenashbf 7.6% were mixed with 363 grams of diisobutylphenol (ratio of "equivalents 1.7) 3.116.2800 grams of water and heated to 60 C. About 1042 grams of BaO were then added and; the temperature was raised to 94-98 C. and held there for 1 hour. The temperature was "then raised to"1'50 C. over a 4 hour period and maintained at that level'forl hour. About 316.:grams ofthetotal mixture were removed and the. product obtained by filtering, product ;A,: containedithe following analysis:

Product A Basic No 63.'0 Percent sulfate ash 19.5 Metal-ratio --3.-18

The remainderofthe unfiltered mass, about. 5296 grams, was blown withabout 330 grams 0f.SO2 at about 170 ,C.,.and until themass was slightly The total weight gain of the masswas 266 grams. The mixture was then filtered and the product identified as product B contained the following analysis:

Product-B Basic No 4.5 Percent sulfate ash 29.0 Metal ratio 5.35

Clearly, the increase in metal contentby virtue of treating'with- S02 is from 19.5 to 29.0%..ona sulfate ash basis.

As mentioned hereinabove, the salt complexes can alsobe prepared by combining the oil-soluble metal sulphonate and inorganic metal compound in the presence of the sediment which forms Occasionally in some of the methodsillustrated above. The following examples illustrate the utility of the sedimentfor preparing salt complexes for the present invention.

EXAMPLE 43 held atthat level for-one hour. Thereafter, the

temperature was raised-slowly Grand held there for aboutpne hour. The rtotalsm-ix-ture was allowed to .settle .orernight, .-fo1lowe d by .decantation and filtering. this experiment 450 grams ofsediment were-produced. The. salt-complex was. aviscous liquid, light-brown incolor and contained-a slight odor. The following, properties ofthe. product were determined:

Basic "No 59.5 Percent sulfate ash 212 Metal ration"; 3.20

19 The sediment obtained in Example 43 was employed in the preparation of a salt complex in the method given in the following example No. 14.

EXAMPLE 44 1700 grams of a 30% oil solution of barium petroleum sulphonate having a 7.6% sulfate ash, 20 grams of phenol, 450 grams of sediment obtained from the preparation given in Example 43, 710 grams of water and 261 grams of barium oxide (barium oxide added slowly) were mixed together and heated to a temperature of 100 C. for about one hour. The total mixture was then raised in temperature in a slow manner to about 150-160 C. and held there for one hour until substantially all the water was removed. The salt complex was separated by filtration and was found to be a viscous liquid, light brown in color, and contained a slight odor. The following properties were determined for the salt complex:

Basic No 82.6 Percent sulfate ash 26.4

The salt complexes formed with oil soluble petroleum sulphonic acid compounds possess exceptionally high metal ratios as compared to those complexes which are obtained when using other oil soluble organic acids. Consequently, in determining the maximum amount of barium metal which can be incorporated into a complex prepared by conventional techniques, the barium petroleum sulphonate was employed for such a purpose. Pursuant thereto, Examples 45 and 46 given below serve to show the highest amount of barium metal which can be incorporated into a salt complex by a conventional technique.

EXAMPLE 45 2500 grams of a 30% oil solution of barium petroleum sulphonate containing 7.6% sulfate ash were heated to 95 C. and a slurry of barium oxide containing 386 grams of barium oxide and 1215 grams of water was added thereto. The mixture was stirred for one hour at a temperature of 100 C. and then heated slowly over a period of three hours to a temperature of 150 C. This temperature was maintained for about one hour until substantially all the water was removed. The salt complex thus produced had the following properties:

Basic No 38.4

Percent sulfate ash 16.0

Metal ratio 2.25

EXAMPLE 46 In this example the procedure employed in Example 45 was followed except that the dehydration step was conducted at a temperature of 200 C. for a period of /2 hour. The p-roduct obtained had the following properties:

Basic No 29.0 Percent sulfate ash 15.3 Metal ratio 2.16

From the above Examples 45 and 46, it can be seen that salt complexes obtained by conventional techniques will only contain a barium metal ratio as high as 2.25 or approximately 2.3. By comparison, the product obtained in accordance with the present invention will in every instance wherein a substantial amount of excess inorganic barium compound is employed, produce products containing more metal than is possible by conventional techniques. Therefore, in every instance where the salt complex is treated with an acidic material and then distilled so as to remove substantially all of the promoter material, the remaining salt complex which constitutes essentially the combination of promoter-free salt complex and the acidic material will have a higher ratio of total metal to normal salt of sulphonic acid. than is possible under conventional techniques. In the examples given hereinafter, it will be shown that the treatment of a salt complex with an acidic material does not significantly effect the metal content of the complex. Furthermore, it will be shown in those examples that the distillation of the acidic material treated complex to recover the promoter does not effect the metal content of the complex.

In another pair of experiments, a comparison was made between the process of the present invention and a conventional process, when using duplicate amounts of components. It is clearly evident from the following examples that this invention will give substantially better results with respect to metal concentration of the complex than is obtainable by the conventional technique.

EXAMPLE 47 The complex was separated by filtration and had the following analyses:

Basic No 85.2 Percent, sulfate ash 25.5 Metal ratio 4.12

EXAMPLE 48 1530 grams of a 30% oil solution of barium petroleum sulphonate having a 7.6% sulphate ash were mixed with 725 ml. of water at about 60 0. Then 271 grams of BaO were added. The temperature of the mixture was raised to -105" C. and held there for one hour while insuring thorough mixing. Thereafter the temperature was raised to 150-160 C. and held there 'for one hour to substantially remove all the water. The complex was separated by filtration and'had the following properties:

Basic No 36.0 Percent sulfate ash 15.34 Metal ratio- 2.14

In all of the foregoing examples, the ratio of equivalents of the organic acid or salt thereof to the promoter has been within the preferred range, viz. 1.5-3.5 to 1. The following examples illustrate the preparation of end-products wherein the ratio of equivalents falls outside of said preferred range, but comes within the broad range found to be operable.

EXAMPLE 49 1000 grams of a 30% oil solution of barium petroleum sulphonate containing 7.6% sulphate ash were mixed with 750 grams of water at 50 C. 282 grams of BaO were added thereto, followed by the addition of a slurry consisting of 460 grams of water, 87 grams of BaO, and grams of para-tertiary-butyl phenol (ratio of equivalents of sulphonate to phenolic compound is 21 0.77). The mass wasv stirred for hour at about 100 C., then it was heated to 200 C. and maintained at that temperature for 2 hours.

The salt complex was separated by filtration. It was a red-brown, viscous liquid, and had the following properties:

Basic No 46 Percent sulfate ash 27.9 Metal ratio 5.4

EXAMPLE 50 2760 grams of a 30% oil solution of barium petroleum sulphonate containing 7.6%sulphate ash were mixed with 217 grams of BaO, 580 grams of water and 41 grams of diisobutenyl sulphonic acid inthat order. The ratio'of equivalents of sulphonate to sulphonic acid is 9.

The mass was heated for one hour at about 100 C., then the temperature was raised to 150 C. and maintained there for one hour. The salt complex was separated by filtration. It was a viscous, brown liquid, and had the following properties:

Basic No 34 Percent sulfate ash 17.3 Metal ratio 2.4

As previously indicated, the immediate product formed by the use of the promoter material may be modified to recover therefrom a substantial portion of the promotor material used by treating such immediate product with a sufficient amount of an acidic material which in the presence of the mass will form a material having a higher ionization constant than the promoter used in the preparation of the immediate product. The promotor is liberated in the form of an organic compound AH containing a substantial portion of the anionic radical of the promotor material. After a portion of the promotor material has been thus regenerated by treating the immediate product with an acidic material, the regenerated promotor may then be separated therefrom by any one of the several known means, or the regenerated promotor material may be left in the mass and the latter then treated with an additional amount of a salt-forming material, and it will be found that the concentration of the stably held metal can be further increased. The following are examples of such further steps in our process.

EXAMPLE 5 1 The salt complex produced in Example 39 was mixed with 1239 grams of mineral oil and heated to a temperature of 190 C. While maintaining this temperature fora period of 1 /2 hours, CO2 was blown through the mixture. The temperature was then lowered to 150 C. continuing the passage of CO2 through the mixture and the basic number of the mixture was tested every minutes, until the analysis showed a basic number of 2.5. The salt complex CO2 product was then separated and was found to be liquid in consistency, brown in color, and contained a very slight odor. The following properties were determined for the product:

Basic No 2.5 Percent sulfate ash 23.2

By comparison, the product of Example 38 contained a sulphate ash of 23.8% whereas this same product after blowing with CO2 contained a sulphate ash of 23.2. Therefore, it can be seen that the metal content of the salt complexis substantially the same after treatment with CO2.

EXAMPLE 52 6043 gramsof the salt complex prepared inaccordance with Example 9 were;.p1aced inazsuitable vessel and CO2 gas was injected at the-bottom of the vessel ata rate of 3750 cc; per minute for a period of 1 hours. During this period, the temperature was in the rangeof 30-'.70-C. At' the end of the blowing. operation the product weighed 6346grams,:showing ag'gain inuweight of 303 grams. The vproduct'wasfiuid, darlrred in color, and contained no odor. The following properties were determined for. the salt complex- CO2 product:

Basic No 24.3 Percent sulfate ash 22.7

Itcan be seen, therefore, bythe gain in weight of the product that the CO2 actually enters into combination with the salt complex. Furthermore, the metal content-of the product is substantially the same as the salt complex prior to beingblown with CO2, since the sulfate ash content is substantially the same as before CO2 treatment.

EXAMPLE 53 1288 grams of the salt-complex prepared in accordance with the method of-Examp'le'5 were blown with CO2 at a temperature of 30-50"C. until the product showed an acid-reaction. Following this CO2 treatment,'the'product was blown with nitrogen for a-period of 15 minutes. "The product thus produced was very viscous; reddishbrown in color, and did not contain-any odor. The following properties were-"determined:

Acid No 5136 Percent'su'lfate ash 17:94

The above examples clearly show that it is-possible to treat the salt complex with an acid anhydride gas and obtain a product which is definitelyacid. Further, treatment with an acid anhydride gas to such extent does .not change the metal content of the salt complex.

Another salt complex product which was blown with CO2 is given in Example 54 below:

EXAMPLE 54 2500 grams of a 30% oil solution of barium petroleum sulphonate containing 7.6% sulfate ash were mixed with 45.6 grams of phenol, (ratio of equivalents is 3.36) and heated to C. A slurry of barium oxide containing 422 grams of barium oxide and 1125 ml. of water was added to the mixture, with stirring, and held at a temperature of 97102 C. for a period of one hour. The temperature was then slowly raised over a period of three hours to C. and maintained at that level for an additional period of one hour until substantially all the water was removed. The desired salt complex was separated by filtering and was found to be an oily liquid, brown in color, and contained a faint odor. The following properties were determined:

Basic No 60.6 Percent sulfate ash 22.3 Metal ratio "3.34

EXAMPLE 55 1250 grams of the salt complex produced in accordance with the method given in. Example 54 above were blown with CO2 for approximately two hours at a temperature below 60 C., until an acid number of 5.0 was obtained. Thaweigh-t of product obtained was 1260 grams.

The COz-salt complex product was then heated at a temperature of 190 C. under a vacuum of mm., producing a distillate weighing about 10 grams. The distillate was then dissolved in iso-propyl ether and then dried over sodium sulphate, filtered and then the sulphate was re-- moved by evaporation. 5 grams of residue remained. This residue was found to be mostly phenol, thus indicating that treatment of the salt complex with an acidic material dissociates at least a portion of the promoter from complex formation.

After the distillation step, the following properties for the salt complex were determined:

Basic No 2.96 Percent sulfate ash 22.4

The percent sulphate ash of the COz-salt complex product indicates that little or no metal is removed from the complex as a result of the CO2 treatment and the distillation step to recover the promoter.

- EXAMPLE 56 1440 grams of the salt complex obtained by the method given in Example 43 were blown with CO2 for about two hours at a temperature of 30-60 C. until the product showed an acid No. of 6. The product thus obtained was then heated at a temperature of 200 C. under vacuum of 4 mm. to recover approximately grams of phenol. The residue of the distillation was a viscous liquid, light brown in color, and containing a, slight odor. This product possessed the following properties:

Basic No 1.06 Percent sulfate ash 22.6

Here again, it is shown that the treatment of the salt complex with an acidic material dissociates the promoter from complex formation in the salt. On a quantitative basis, it was determined that approximately of the original phenol was still held in complex formation in the CO2 treated product.

The salt complex prepared in accordance with Example 57 below was treated with S02 as shown in Example 58 which is also given below.

EXAMPLE 57 6000 grams of a solution of barium petroleum sulphonate (sulfate ash 7.6%), 348 grams of para-tertiary butyl phenol (ratio of equivalents is 1.70) and 2915 grams of water were mixed and heated to a temperature of 60 C. 1100 grams of barium oxide were added slowly and the temperature of the total mixture was raised to 94-98 C. and held there for one hour. The temperature of the mixture was then slowly raised over a period of 7 /2 hours to about 150 C. and held at that level for an additional hour until substantially all the water was removed. The salt complex obtained is. a liquid, brown in color, and did not contain any odor. The'following properties were determined:

Basic No 82.5 Percent sulfate ash 26.0 Metal ratio 4.2

EXANIPLE 58 24 number of 0. The SOs-salt complex product was liquid, brown in color, and did not contain any odor.

An experiment was conducted in order to determine whether air, which contains CO2, would be effective as an acidic material. The examples below illustrate the utility of air for this purpose.

EXAMPLE 59 380 lbs. of a 30% solution of barium petroleum sulphonate having a 7.6% sulfate ash, 21.9 lbs. of para-tertiary-butyl phenol and 184 lbs. of water were combined and heated to 51 C. 68 lbs. of BaO were then added, and th temperature varied from about 51 C. to 64 C. over a period of about 1 hours. The temperature was then raised to C. and held there for 1 hour. Then the temperature was raised to 153 C. over about 4 /2 hours and. held at that level for 1 hour. The complex was obtained by filtration and was found to have the following analysis:

Basic No 80.5

Percent sulfate ash 26,0

Metal ratio 4.2

EXAMPLE 60 6000 grams of the product obtained in the above example, No. 59, were heated to C. and blown with air for a period of about 13 hours. The final product contained a basic no. of 1.1 and analyzed a 26.4% sulfate ash. It can be seen therefore that air can also be classified as an acidic material, because it lowered the basic no. and did not significantly change the metal content.

In all of the above examples the mahogany soap is referred to as barium petroleum sulphohate, and likewise the mahogany acid is similarly designated as petroleum sulphonic acid.

Th oil-soluble barium sulphon-ates and/or oil-soluble sulphom'c acids The oil soluble barium sulphonates and/or sulphonic acids can be of the cyclic 0r aliphatic types. The cyclic compounds include the mono or polynuclear aromatic or cycloaliphatic compounds.

The oil soluble compounds can be represented by the following formulae:

In the above formulae, M is either barium or hydrogen; T is a cyclic nucleus such as for example benzene, naphthalene, anthracene, phenanthrene, diphenylene, thioanthrene, phenothioxine, dip-henylene sulphide, diphenylene oxide, diphenyl oxide, diphenyl sulphide, diphenyl amine, cyclohexane, petroleum naphthenes, decahydronaphthalene, cyclopentane, etc.; R. is an aliphatic group such as alkyl, alkenyl, alkoxy, alkoxyalkyl, carboalkoxy-alkyl, etc. groups; a: is at least one, and Rx contains a total of at least about 15-18 carbon atoms. R in Formula II is an aliphatic radical containing at least about 15-18 carbon atoms and M is either barium or hydrogen. Examples of types of the R radical are alkyl, alkenyl, alkoxyalkyl, carboalkoxyalkyl, etc. Specific examples of R are petrolatum, saturated and unsaturated paraffin wax, polyolefins including poly C3, C4, C5, C6, C1, C8, etc. olefin hydrocarbons.

The groups T, R, and R in the above formulae can also contain other organic or inorganic sub- 25' stituents in addition to those enumerated above, such as for example, hydroxy, mercapto, halogen, nitro, amino, nitroso, carboxy, ester, ether, etc.

In Formula I, x, y, z and b are at least one, and likewise in Formula II, a, b, and d are at least one.

The following are specific examples of oilsoluble sulphonic acids coming within Formulae I and II above, and it is to be understood that such examples serve to also illustrate the barium salts of the sulphonic acids. In other words, for every sulphonic acid enumerated, it is intended that the barium salt thereof is also illustrated.

Such sulphonic acids are mahogany sulphonic acids; petrolatum sulphonic acids; monoand polywax substituted sulphonic and polysulphonic acids of e. g: naphthalene, phenol, diphenyl ether, naphthalene disulphide, diphenyl amine, thiophene, alpha-chloro-naphthalene, etc.; other substituted sulphonic acids such as cetyl-chlorobenzene sulphonic acids, cetyl-phenol mono-sulfide sulphonic acids, cetoxy capryl-benzene sulphonic acids, dicetyl-thianthrene disulphonic acid, di-lauryl beta-naphthol sulphonic acids, di-capryl nitro-naphthalene sulphonic acids; aliphatic sulphonic acids such as paraflin wax sulphonic acids, unsaturated paraffin wax sulphonic acids, hydroxy substituted paraffin wax sulphonic acids, tetraisobutylene sulphonic acids, tetraamvlene sulphonic acids, chloro substituted parafiin wax sulphonic acids, nitroso paraliin wax sulphonic acids, etc.; cyclo-ali'ohatic sulphonic acids, such as petroleum naphthene sulphonic acids, cetyl-cyclopentyl sulphonic acids, laurylcyclohexyl sulphonic acids, bis (diisobutyl) cyclohexyl sulphonic acids, monoor polywax substituted cyclohexyl sulphonic acids, etc. Additional examples of oil soluble sulphonic acids and/or barium salts thereof which can be used as starting materials are disclosed in the following U. S. patents: 2,174,110: 2,174,506; 2.174508; 2,193,824;

2,197,800; 2,202,791; 2,212,786; 2,213,360; 2,228,598; 2,233,676; 2,239,974; 2,263,312; 2,276,090; 2,276.097; 2,315,514; 2,319,121; 2,321,022; 2,333,568; 2,333,788; 2,335,259; 2,337,552; 2,346,568; 2,366,027; 2,374,193; and 2,383,319.

With respect to the sulphonic acids or barium The promoter The promoter employed in the process of this invention can be the organic compound AH wherein H is hydrogen and A is an anionic organic radical and/or the barium salt thereof. More particularly, the organic compound AXH is employed, wherein A and H are defined as given above for the compound AH and X is oxygen or sulfur. Also, the barium salt of AXH can be used alone or in'admixture with the compound AXH. The compounds AH or AXH should have ionization constants measured in water at 25 C. greater than about 'lXlO- water solubilities of at least about .0005% of 50 C. and saturated aqueous solutions 'of which exhibit a pH not greater than's'ev'en.

Generally, it is found that phenolic compounds, ionizable organic nitro compounds, e. g. nitroparaffins, lower molecular weight aromatic carboxylic acids, lower molecular weight organic .thiophosphoric acids, the lower molecular weight sulphonic acids, hydroxy aromatic compounds, lower molecular weight hydroxy aromatic acids, etc, are suitable for the purposes of the present invention.

For the purpose of this specification and the appended claims, it should be understood that the phenolic compounds includes those compounds in which a hydroxyl group is directly attached to a benzenoid carbon atom, and which compounds may or may not contain other substituent groups. A phenol is referred to hereinafter as a subclass of phenolic compounds in which a single hydroxyl group is directly at-- tached to a benzenoid carbon atom, and which compound may or may not contain a hydrocarbon group or plurality thereof in addition to said hydroxyl group. To better illustrate the wide variety of classes of compounds which can be employed in forming a salt complex in accordance with the present invention, specific examples are enumerated below. It is to be understood that while only the organic compounds AH are illustrated, it is intended that the barium salts thereof are included as specific examples.

The promoters found useful as promoters are phenol; alkylated phenols such as, for example. cresol, xvlenol, p-ethyl phenol, di-ethyl phenols. n-propyl phenols, di-isopropyl phenols, p-t-butyl phenol, p-t-amyl phenol, p-cyclopentyl phenol, sec-hexyl phenols, n-heptyl phenols, diisobutyl phenols, 3,5,5-trimethyl-n-hexyl phenols, n-decyl phenols, cetyl phenols, etc.; aryl substituted phenols, e. a. phenyl phenol, d-iphenyl phenol, etc.; polyhydroxy aromatic compounds such as alizarin, quinezarin or polvhydroxy benzenes, e. g., hydroquinone, catechol, pyrogallol, etc.; monohydroxy naphthalenes, e. g. a-naphthol, B- naphthol, etc.; polyhydroxy naphthalenes, e. g., naphthohydroouinone. naphthoresorcinol, etc.; the alkylated polyhydroxy aromatic com ounds such as octyl catechols. mono-(tri-isobutyl) yrogallols, etc.;' substituted phenols such as p-nitro phenol, picric acid, o-chlorophenol, t-butyl chloronhenols, p-nitro-o-.ch orophenol, p-amino phenol, etc; lower molecular weight hvdroxy aromatic carboxvl'ic acids such as salicylic acid, chloro salicylic acids, d-i isopro ovl salicylic acids, gallic acid. 4-hvdroxy-l-nanhthoic acid, etc.: lower molecular wei ht aromatic sul hon c i acids such as: p-cresol sulphonic acid, p t-butyl phenol sul honic acid, beta-naohthol alpha-sulphonic acid, etc.; lower molecular wei ht aromatic acids such as benzoic acid, p-nitro benzoic acid, o-chloro benzoic acid, p-toluic acid, p-t-butyl benzoic acid, alpha nanthoic acid, vetc.; lower molecular wei ht aromatic sulphonic acids such as benzene sulphonic acid, p-chloro'benzene sulphonic acid, p-nitrobenzene sulphonic acid,v

etc.; lower molecular weight thiophosphoricacids e. g., tolyl mon'othiophosphoric acids, isopropylphenyl monothiophosphoric acid, diisopropyl dithiophosphoric acids, etc.

- Additional examples of lower molecular weight sulphonic acids and/or corresponding barium salts which can be used as promoters are disclosed in the following U. S. patents: 2,174,110;

2,321,022; 2,333,738; 2,335,259 and 2,337,552.

However, it is to be understood that the aboveenumerated promoters are not equivalent, but that under certain conditions some are more effective than others.

Inorganic barium compounds The salt complexes of the present invention are formed with an inorganic barium compound wherein the anionic radical, may be for example, hydroxyl, oxide, carbonate, bicarbonate, sulphide, sulfite, hydrosulphide, halide, hydride, amide, basic carbonate, etc. Of the inorganic barium compounds, good results are obtained with those having a water solubility of at least about 0.0003% at 50 C., and preferably at least about 0.006%. In a preferred instance, excellent results are obtained with the inorganic compounds of the basic type, that is, those com pounds which in saturated aqueous solutions give an alkaline reaction, i. e. which have a pH value greater than 7.

To further illustrate the large number and variety of classes of inorganic barium compounds which can be employed, specific examples thereof are enumerated below.

The inorganic barium compounds include for example barium oxide, barium hydroxide, barium sulfide, barium carbonate, barium bicarbonate, barium hydride, barium amide, barium chloride, barium bromide, barium nitrate, barium sulfite, barium hydrosulfide, barium borate, etc. The corresponding basic salts of the just enumerated compounds are also intended.

Acidic material As previously indicated, one form of the process of the present invention includes the step of treating the immediate product with an acidic material, which is defined herein as a material which possesses acidic characteristics when present in the mass containing the complex. This treatment effects the liberation of at least a portion of the material previously referred to as the promotor. A particularly effective acidic material which has been utilized for this purpose is carbon dioxide. We are aware of the fact that Mertes in his Patent No. 2,501,731 suggested transforming a sodium hydroxide-calcium sulphonate complex into the sodium carbonatecalciumsulphonate complex or the corresponding bicarbonate complex by blowing the hydroxide complex with carbon dioxide at elevated temperatures.

In our process, the step of treating with an acidic material such as CO2 or air has the effect of liberating from the immediate complex product formed at least a portion of the promoter used. Thus the presence in the immediate com-- plex product of the promoter material, in com bined form, clearly distinguishes the immediate product from any organic metal complex type material heretofore produced. Moreover, the nature of the product formed by regenerating from the immediate product at least a portion of the promoter material leaves that product with a composition which is quite different from the other prior art organic metal complexes previously produced. It is recognized that in accordance with the present invention, the promoter in the form of a barium salt can be used; however, notwithstanding, upon treating the complex with an acidic material, the salt used as a promoter is freed from association in the complex as the metal-free promoter and not the barium salt.

For the purpose, that is, of releasing the promoter from the complex, an important feature or characteristic of the acidic material is that it must, when present in the mass containing the complex, possess an ionization constant greater then the organic compound used as the promoter. Thus for the purpose of this specification and the appended claims, it is to be understood that the acidic material can be either-a liquid, gas or solid prior to being incorporated in the mass which contains the salt complex.

The acidic material usually employed is a liquid or a gas. The liquids can include the strong or weak acids, such as for example hydrochloric, sulphuric, nitric, carbonic acid, etc.; where as the gas is for the most part an anhydride of an acid or an acid anhydride gas.

The following are additional specific examples of acidic materials, viz.: E01, S02, S03, CO2, air (considered acidic because of CO2 content), N02, H28, N203, PCls, S0012, C102, I-IzSe, BFs, CS2, COS, etc.

It is to be understood, however, that all the acidic materials are not equivalent, but that under certain conditions, some are more effective or desirable than others.

Process conditions The salt complex of the present invention is prepared by combining the aforementioned compounds in the presence of water. The water can be present as a result of addition thereof to the mixture, or liberated from either the essential components or other additionally present compounds, as a result of being subjected to heat. However, it is preferred to add water to the mixture to effect salt complex formation. It has been found that the metal complex can be prepared when using small quantities of water, such as about 1 mole of water per mole of inorganic barium compound. However, more usually about 5 to 50 moles of water per mole of inorganic barium compound are used, and preferably about 15 to 30 moles per mole.

Generally, the complex obtained from using the inorganic barium compound, the oil-soluble sulphonic acid and/or the barium salt thereof, and the promoter, is prepared by heating the components in the presence of water at a superatmospheric temperature while insuring thorough mixing, and then still further heating said mixture to substantially remove all of the water. At least five methods are available by which the complex can be formed, namely:

(a) The promoter is added to the oil-soluble normal salt of sulphonic acid, followed by an addition of an aqueous solution or suspension of the inorganic barium compound thereto, the mixture is held at a superatmospheric temperature for a reasonable length of time while effecting thorough mixing, and then the total mixture is further heated to remove substantially all the water;

(1)) The inorganic barium compound in a dry state is added to a mixture of sulphonic acid or normal sulphonate, promoter and water, heating while insuring thorough mixing and then further heating to remove substantially all of the water;

The acid of the desired sulphonate is mixed with the promoter, then an aqueous solution or suspension of the inorganic barium compound is. added thereto, the mixture is heat edand agitated at a superatmospheric temperature for a time sufficient to insure thorough mixing and followed by subjecting the total mixture to dehydration conditions in orderto remove substantiallyall of the water;

(-d) In all of the methods described-herein, the mixture containing the complex product is treated with an acidic materialjust, prior ,to, filtering, and then the desired complex is separated from other uncom-bined materials; and

(e) The sediment formed from any of the aforementioned methods can be employed either alone orwith additional promoter: inrany ofthe three methods givenabove.

In all of the methodsd-escribed above for pre paringpthesalt complex, the step of removing substantially all of the water is accomplished at a temperature not substantially in'excess of 350 C., preferably about l10to 200 C; The technique employed to'remove the water includes for example a conventional flash strip-ping operation, which involves passing the material in a thin film state over a large heated area-of fglass, ceramic or metal heatin under subatmospheric pressures; as well as heatingunder either atmospheric or superatmospheric pressure; It can therefore be seen that'the temperature as Well as the time for effecting substantial removal of water will vary considerably, depending on the technique employed therefor. Generally, the time required to effect substantial removal of water, when employing drying other than flash techniques, is about 15 minutes or less, and can be as high as 10-15 hours. Usually; however, it is most convenient to employ atmospheric pressure for such an operation, and consequently it requires about 1 to 5 hours to remove substan-. tially all of the water. At 'a laterstageof the process, the acidic material when used in gaseous form maybe used to removethe last portion of water.

For the purposes of this specification and the appended claims, the relative chemical equivalents of oil soluble sulphonic acid and/or-barium salt thereof "and promoter is expressed as the ratio of equivalentsnof the former to'the latter.

In accordance therewith, the ratio of equivalents of oil soluble sulphonic acid and/or barium salt thereof to promoter is from about,1. to to about lOto 1, preferably from about 3 to 2 to about. '7 to 2.

The amount of inorganic barium compound employed, generally; will be sufilcient to have.

present in the total mass at least more than about one equivalent of barium regardless of how combined, per equivalent of oil soluble sulphonic acid and/or barium salt thereof plus promoter. Inother words, the amount of inorganic barium compound employed must be such that there is more than enough to theoretically form merely a normal salt of oil soluble sulphonic acid and a barium salt of the promoter. Thus, for the purposes of this specification and the appended;

claims, the amount of inorganic barium compound employed will be expressed. as in an amount such that there are presentin the. mass substantially more .than onaequivalent. of. baricomplex can-be significantly increased byztreat ing the mixture with an acidic material prior:v to filtering same to recover-"the -desired-.;product or salt complex. In general, about 0.5 to 20% of the acidic material, based on the weight of the total mass; is employed at a temperature not.substan-= tially in excess of 350 C., more-usually about 25 to 250 C., and. preferably 50 to C., and for a period of about 0.25 to 30 hours. The time of treatment varies considerably depending on the results desired and the type of acidic material employed. Treatment with, an acidic anhydride gas may be accelerated by superatmospheric pressure.

As indicated hereinabove, treatment of the Sept arated salt complex product with an acidicmateri-al is done in instances where it is desirable to lower the basic number of the salt complex and/or partially orsubstantially completelyrecover the promoter. This treatment is effected at a temperature of about 25 to 250 C., preferably about 50 to 170 C., and by usually employing about 0.5 to 20 of acidic material, based on the weight of salt complex. The time of treatment with the acidic material can vary considerably, depending'on the desired result. As would be expected, short periods of treatment will cause only partial liberation or release of the promoter or small decreases in the .basic number of the salt complex. However, in general, periods of treatment will range from about 0.25 to 30 hours.

In most cases, and particularly Where it is desired to recover the promoter, the amount of acidic material used should be at least equivalent to the amount of metal present as the salt of the ionizable form of promoter.

Whenit is desired to produce a product having substantially neutral reaction, the amount of acidic material used should be at least equivalent to the total metal in excess of that present as the normal salt of the oil soluble organic acid.

As indicated above, in order to facilitate anunderstanding of the .amount of metal which can be present in the salt complex, the metal ratio isdefined as the ratio of the total metal in the salt complex to the amount of metal which is in the form of a normal salt of the oil-soluble sulphonic acid. In accordance therewith, the salt complex formed with the oil-soluble sulphonic acid and/or barium-salt thereof, the promoter and the inorganic barium compound include metal ratios greater than 1 and up to about 10 or:

more. As for the complex which is treated with an acidic material, the metal content is substantially the same as in the complex prior to treating. Consequently, the same metal ratio as given above will apply to such treated products. In

bined. It is to be understood, howeverythat such.

31 theories are advanced for the purpose of offering explanations, and are not to be construed as limitations on the scope of the present invention.

In the following equations, AXH represents a promoter in which H is an ionizable hydrogen and M represents a divalent metal. Assuming that the promoter may act as a catalyzer for the formation of inorganic polymeric configurations, viz. (-MO):H, which are bonded to the acid group, (e. g. the sulphonate radical in the preferred instance), the possible reactions that may occur with the sulphonate radical are:

1) 2RS03HI+ orm RsomM 21120 2) Rs03)2M+M H)i ZRSOZIVI-OH Oatalys The resultant complex, according to the above theory, can be a complex mixture of all the potential products listed above. It is apparent that high metal ratios are possible under this theory.

Another theory is based upon an electronic interpretation. For example, in the case of the neutral sulphonate, the charges are distributed as follows:

The electron octets around the two oxygen atoms which are not attached to a metal atom ive to each of these atoms a unit negative charge, thus leaving the sulfur atom with a double positive charge.

When the sulphonate, excess inorganic metal compound, promoter and water are reacted according to the present invention, a basic promoter salt, AX-M-OH is presumed to be formed. This normally oil-insoluble salt dissolves in the reaction mixture because of the electronic attracting force known as a hydrogen bonding. structurally this can be shown as:

(b) H O-M-XA Structure (a) would have a metal ratio of 3.0, and structure (1)) would have a metal ratio of 5.0. Combinations of neutral sulphonate and one or both structures would explain the whole number and fractions of metal ratios which are obtained in actual practice.

After the structure (a) and (b) are formed, if hydroxyl ions are present in the reaction mass the following reactions may take place:

0-...H... O-M-OH The AX- ions may then react with M OH 2 to produce more AXMOH, and the latter would in turn lead to the formation of additional amounts of structures (a) and (b). The cycle may occur repeatedly.

According to this electronic explanation, the AX residue of the basic promoter salt appears to function as a carrier for the M (OI-D2, and thus facilitating the communicating of the M(OH)2 into close positions with the negatively charged oxygen atoms of the sulphonate radical.

Having thus described the present invention by furnishing specific examples thereof, it is to be understood that no undue limitations or restrictions are to be imposed by reason thereof, but that the scope of this invention is defined by the appended claims.

The salt complexes produced in accordance with the present invention can be employed in lubricants including oils and greases, and for such purposes as in crankcases, transmissions, gears, etc., as well as in torque converter oils. Other suitable uses for such complexes are in asphalt emulsions, insecticidal compositions, fire-proofing agents in plasticizers and plastics, paint driers, rust inhibiting compositions, pesticides, foaming compositions, cutting oils, metal drawing compositions, flushing oils, textile treatment compositions, tanning compositions, metal cleaning compositions, emulsifying agents, antiseptic cleansing compositions, penetratingagents, gum solvent compositions, fat splitting agents, bonding agents for ceramics and asbestos, asphalt improving agents, flotation agents, improving agents for bydrocarbon fuels such as, e. g., gasoline and fuel oil, etc.

More particularly, the complexes of this invention are especially adapted for the preparation of lubricants, paint driers and plastics, especially the halogen bearing plastics. In these respects, the salt complex can be employed in the following concentrations based upon the weight of the total composition.

Broad Usual Preferred range range range' Percent Percent Percent Lubricants 0. 01-20 0. 2-15 0. 5-10 Stabilizing agent for plastics 0. 05- 5 0. l- 3 0. 2- 2 Paint Drier 0.2 25 0. 5-20 1.0-15

V 0.25, Barium di-lauryl dithiophosphate 0.75'

emraoeo '33 Useas a; stabiliz ng agentfor'halogen'-bearing plastics:

Poly-vinyl chloride 7010 -Di'-octyl 'phthalate i- 1 28. 75 Product of Exam-ple 1 41mm; 125

'Use asa paint drier:

Titanium-base house paint. 197.0 Product of Example 19 3.0

(other modes of applying the principle of the invention may be employed, change beingmade as'regards the detailsdescribed, provided thefeatures stated in any of the-following claims,=-or"-the equivalent of such be employed.

We therefore "particularly point out and "distinctly'claim as our invention:

l; A' process which comprises preparing and mixing a mass in which, at-50C., at least 50% of'th'e components are in the -liquid-state,-and in which mass th'eactive components consist of:

A. Anorganic compound selected from the class consisting .of oil-soluble organic sulphonic acid compounds havinga total of at least 18 carbon atoms and the barium salts thereof;

B. An organic compound selected from the class "consisting of phenolic organic compounds and the barium salts thereof, said organic compound having:

(a) An ionization constant in water of at least about 1 10-- at about C.; ('b) A water -solubil-i-ty at C. of at least I about ().-0005-% and (-c) Insaturated aqueous-solutions atabout 25C. a-pH-ofless that-1 7;

the relative amounts of A andBuised beinginthe rangeo'f from about one equivalent of A to about 10 equivalents of B to about 10 equivalents of A to about one equivalent of B;

C. An inorganic barium compound;

(1) Which is water-soluble at a temperature of 50 C. to the extent of at least about 0.0003%;

(2) In an amount such that there are present in the mass substantially more than 1 equivalent of barium, including the barium present in the remaining components, per equivalent of A plus B; and

D. Water, in an amount equal to at least about one mole per mole of C;

maintaining the mass at a temperature and for a period of time suflicient to drive ofi substantially all free water and water of hydration which may be present, and form the organic barium complex; and then treating the organic barium complex with carbon dioxide in amounts sufiicient to liberate a substantial proportion of said organic compound of component B.

2'. A process in accordance with claim 1 characterized further in that the organic sulphonic acid compound which is component A is an oilsoluble organic sulphonic acid.

3. A process in accordance with claim 1 characterized further in that the organic sulphonic acid compound which is component A is an oilsoluble cyclic sulphonic acid.

4. A process in accordance with claim 1 characterized further in that the organic sulphonic acid compound which is component A is an oilsoluble aromatic sulphonic acid.

5. A process in accordance with claim 1 characterized further in that the organic sulphonic acid compound which is component A is an oil- 34 soluble aliphatic substituted single .rin'gz aromatic sulphonic acid.

"'6. A process inac'cordance with claim 1 characterized-further thatthe organic sulphonic acid compound which iscomponent A is an oils'oluble alkyl substituted benzene ringsulphonic acid containing at least "15 alkylcarbon atoms.

7. A process in accordance with-claim 1 characterized further in that the organic sulphonic acid compound which is component A :is ancilsoluble hydroxy rsub'stitutedsingle ring aromatic sulphonic acid.

8. Aprocess in accordance with claim-L 1 characterized-further in that the organic sulphoriic acid-compound whichIis component A is an'oilsoluble wax phenol-sulphonic acid.

9. A process inacccrdance with claim 1 characterized further in that "the organic :sulphonic acid compound which component is-an oilsoluble cycloaliphatic sulphonic acid.

10. Aprocess in accordance with claim '1 characterized further in tha t the organic sulphonic acid compound which is component A is -an-oi-lsoluble mahogany acid.

11. A process in accordanceav-ith claim l-characterized further inthat "the organic sulphonic acid' compoundwhich is component A isan oilsoluble aliphatic suiphonic acid.

12. A process in accordance withclaim -1 characterized further in that the organic sulphonic acid compoundw'hich' is component-A is an oilsolu'bl straight-chainacyclic sulphonic acid.

13. A processin accordance with claim '1 characterized further in that the organic sulphonic acid compound which is component A is an-oilsoluble chlorinated paraffin wax sulphonic acid.

"14. A process in accordance with claim 1 characterized further in that the organic sulphonic acid compound which is component A is an oilsoluble branched chain acyclic sulphonic acid.

15. A process in accordance with claim 1 characterized further in that the organic sulphonic acid compound which is component A is an oilsoluble chlor-White oil sulphonic acid.

16. A process in accordance with claim 1 characterized further in that the organic compound which is component B is a phenolic organic compound.

17. A process in accordance with claim 1 characterized further in that the organic compound which is component B is phenol.

18. A process in accordance with claim 1 characterized further in that the organic compound which is component B is a not more than 16 carbon hydrocarbon substituted phenolic organic compound.

19. A process in accordance with claim 1 characterized further in that the organic compound which is component B is a lower alkyl substituted phenolic organic compound.

20. A process in accordance with claim 1 characterized further in that the organic compound which is component B is diisobutyl phenol.

21. A process in accordance with claim 1 characterized further in that the organic compound which is component B is tertiary butyl phenol.

22. A process in accordance with claim 1 characterized further in that the organic compound which is component B is a barium salt of a phenolic organic compound.

23. A process in accordance with claim 1 characterized further in that the organic compound which is component B is a barium salt of a not more than 16 carbon hydrocarbon substituted phenolic organic compound.

24.. A process in accordance with claim 1 characterized further in that the organic compound which is component B is a barium salt of a lower alkyl substituted phenolic organic compound.

25. A process in accordance with claim 1 characterized further in that the organic compound which is component B is the barium salt of diisobutyl phenol.

26. A process in accordance with claim 1 characterized further in that the organic compound of component B is a non-metal inorganic substituted phenol.

27. A process in accordance with claim 1 characterized further in that the organic compound of component B is tertiary-butyl chloro phenol.

28. A process in accordance with claim 1 characterized further in that the organic sulphonic acid compound of component A is petroleum naphthene sulphonic acid.

29. A process in accordance with claim 1 characterized further in that the organic sulphonic acid compound of component A is a wax phenol sulphonic acid, and the organic compound of component B is phenol.

30. A process in accordance with claim 1 characterized further in that the organic sulphonic acid compound of component A is mahogany acid, and the organic compound of component B is diisobutyl phenol.

31. A process in accordance with claim 1 characterized further in that the organic sulphonic acid compound of component A is chlorinated paraffin wax sulphonic acid, and the organic compound of component B is tertiary butyl phenol.

32. A process in accordance with claim 1 characterizcd further in that the organic sulphonic acid compound of component A is chlor-White oil sulphonic acid, and the organic compound of component B is the barium salt of diisobutyl phenol.

33. A process in accordance with claim 1 characterized further in that the organic sulphonic acid compound of component A is petroleum naphthene sulphonic acid, and the organic compound of component B is tertiary butyl chloro phenol.

34. As a new composition of matter, an oilsoluble reaction product produced by the process of claim 1, which is substantially free of a. salt of said low molecular weight organic compound of component B.

36. As a new composition, the oil-soluble reaction product mass produced by the process of claim 1, which includes as a component thereof a substantial proportion of the metal-free, low molecular weight organic salt-forming compound of component B liberated from said organic alkaline-earth metal complex.

PETER A. ASSEFF. THOMAS W. MASTIN. ALAN RHODES.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,413,311 Cohen Dec. 31, 1946 2,417,428 McLennan Mar. 18, 1947 2,418,894 McNab et al Apr. 15, 194'? 2,426,540 Watkins et a1. Aug. 26, 194'? 2,459,995 Duncan et a1 Jan. 25, 1949 2,465,221 Gilbert Mar. 22, 1949 2,501,732 Mertes Mar. 28, 1950 

1. A PROCESS WHICH COMPRISES PREPARING AND MIXING A MASS IN WHICH, AT 50* C., AT LEAST 50% OF THE COMPONENTS ARE IN THE LIQUID STATE, AND IN WHICH MASS THE ACTIVE COMPONENTS CONSIST OF: A. AN ORGANIC COMPOUND SELECTED FROM THE CLASS CONSISTING OF OIL-SOLUBLE ORGANIC SULOPHONIC ACID COMPOUNDS HAVING A TOTAL OF AT LEAST 18 CARBON ATOMS AND THE BARIUM SALTS THEREOF; B. AN ORGANIC COMPOUND SELECTED FROM THE CLASS CONSISTING OF PHENOLIC ORGANIC COMPOUNDS AND THE BARIUM SALTS THEREOF, SAID ORGANIC COMPOUND HAVING: (A) AN IONIZATION CONSTANT IN WATER OF AT LEAST ABOUT 1X10-10 AT ABOUT 25* C.; (B) A WATER SOLUBILITY AT 50* C. OF AT LEAST ABOUT 0.0005%; AND (C) IN SATURATED AQUEOUS SOLUTIONS AT ABOUT 25* C. A PH OF LESS THAN 7; THE RELATIVE AMOUNTS OF A AND B USED BEING IN THE RANGE OF FROM ABOUT ONE EQUIVALENT OF A TO ABOUT 10 EQUIVALENTS OF B TO ABOUT 10 EQUIVALENTS OF A TO ABOUT ONE EQUIVALENT OF B; C. AN INORGANIC BARIUM COMPOUND; (1) WHICH IS WATER-SOLUBLE AT A TEMPERATURE OF 50* C. TO THE EXTENT OF AT LEAST ABOUT 0.0003%; (2) IN AN AMOUNT SUCH THAT THERE ARE PRESENT IN THE MASS SUBSTANTIALLY MORE THAN 1 EQUIVALENT OF BARIUM, INCLUDING THE BARIUM PRESENT IN THE REMAINING COMPONENTS, PER EQUIVALENT OF A PLUS B; AND D. WATER, IN AN AMOUNT EQUAL TO AT LEAST ABOUT ONE MOLE PER MOLE OF C; MAINTAINING THE MASS AT A TEMPERATURE AND FOR A PERIOD OF TIME SUFFICIENT TO DRIVE OFF SUBSTANTIALLY ALL FREE WATER AND WATER OF HYDRATION WHICH MAY BE PRESENT, AND FORM THE ORGANIC BARIUM COMPLEX; AND THEN TREATING THE ORGANIC BARIUM COMPLEX WITH CARBON DIOXIDE IN AMOUNTS SUFFICIENT TO LIBERATE A SUBSTANTIAL PROPORTION OF SAID ORGANIC COMPOUND OF COMPONENT B. 